Diazo dyes having a phenylene group as the middle component and a naphthalene group as the terminal diazo component

ABSTRACT

Azo dyes of the formula ##STR1## in which R 1  is hydrogen or substituted or unsubstituted phenylamino, 
     R 2  is hydrogen, amino or N-mono- or N,N-di-C 1  -C 4  alkylamino, 
     R 3  is hydrogen or hydroxyl, 
     R 4  is hydrogen, C 1  -C 4  alkyl, C 1  -C 4  alkoxy, C 2  -C 4  alkanoylamino, ureido or halogen and 
     K is as defined in claim 1, 
     the azo dyes of the formula (1) comprising at least one and not more than two sulfo groups, 
     are particularly suitable for dyeing or printing cellulosic fibre materials or naturally occurring or synthetic polyamide fibre materials with a high dyeing yield, and give dyeings and prints with good fastness properties.

The present invention relates to novel azo dyes, processes for theirpreparation and the use of these dyes for dyeing and printing fibrematerials, in particular textile fibre materials.

The present invention relates to azo dyes of the formula ##STR2## inwhich R₁ is hydrogen or substituted or unsubstituted phenylamino,

R₂ is hydrogen, amino or N-mono- or N,N-di-C₁ -C₄ alkylamino,

R₃ is hydrogen or hydroxyl,

R₄ is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino,ureido or halogen and

K is a radical of the formula ##STR3## in which R₅ and R₆ independentlyof one another are hydrogen or C₁ -C₄ alkyl which is unsubstituted orsubstituted by hydroxyl or phenyl, in which the phenyl radical isunsubstituted or substituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄alkanoylamino, ureido, halogen or sulfo,

and

R₇ and R₈ independently of one another are hydrogen, C₁ -C₄ alkyl, C₁-C₄ alkoxy,

C₂ -C₄ alkanoylamino, ureido, halogen or sulfo;

or a radical of the formula ##STR4## in which Y is hydrogen or C₁ -C₄alkyl which is unsubstituted or substituted by hydroxyl and

R₉ and R₁₀ independently of one another are hydrogen, C₁ -C₄ alkyl, C₁-C₄ alkoxy,

C₂ -C₄ alkanoylamino, ureido, halogen or sulfo;

or a radical of the formula ##STR5## in which R₁₁ is hydrogen, C₁ -C₄alkyl or phenyl which is unsubstituted or substituted by C₁ -C₄ alkyl,

C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino, ureido, halogen or sulfo and

R₁₂ is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino,ureido, halogen or hydroxyl;

or a radical of the formula ##STR6## in which R₁₃ is hydrogen, C₁ -C₄alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino, ureido or halogen;

or a radical of the formula ##STR7## or a radical of the formula##STR8## in which R₁₄ is amino or hydroxyl,

R₁₅ is methyl or carboxyl and

R₁₆ and R₁₇ independently of one another are hydrogen, C₁ -C₄ alkyl, C₁-C₄ alkoxy,

C₂ -C₄ alkanoylamino, ureido, halogen or sulfo;

or a radical of the formula ##STR9## in which R₁₈ is hydrogen or C₁ -C₄alkyl,

R₁₉ is cyano, carbamoyl or sulfomethyl and

R₂₀ is hydrogen, C₁ -C₄ alkyl or phenyl which is unsubstituted orsubstituted by C₁ -C₄ alkyl,

C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino, ureido, halogen or sulfo;

or a radical of the formula ##STR10## in which R₂₁ is hydrogen, C₁ -C₈alkyl or phenyl which is unsubstituted or substituted by C₁ -C₄ alkyl,

C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino, ureido, halogen or sulfo,

R₂₂ is hydrogen or C₁ -C₈ alkyl and

R₂₃ is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino,ureido, halogen or sulfo;

and the azo dyes of the formula (1) comprise at least one and not morethan two sulfo groups,

with the proviso that if R₁ and R₂ are hydrogen and K is a radical ofthe formula (2), the radical R₄ is C₂ -C₄ alkanoylamino or ureido.

C₁ -C₄ Alkyl radicals Y, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃,R₁₆, R₁₇, R₁₈, R₂₀ , and R₂₃ are methyl, ethyl, propyl, isopropyl,butyl, isobutyl, sec-butyl or tert-butyl, in particular methyl or ethyl,where alkyl radicals Y, R₅ and R₆ can be unsubstituted or furthersubstituted as defined above.

C₁ -C₈ Alkyl radicals R₂₁ and R₂₂ are, for example, methyl, ethyl,propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl orstraight-chain or branched pentyl, hexyl, heptyl or octyl, in particularmethyl or ethyl.

C₁ -C₄ Alkoxy radicals R₄, R₇, R₈, R₉, R₁₀, R₁₂, R₁₃, R₁₆, R₁₇ and R₂₃are, for example methoxy, ethoxy, propoxy, isopropoxy, butoxy,sec-butoxy, isobutoxy or tert-butoxy, in particular methoxy or ethoxy.

C₂ -C₄ Alkanoylamino radicals R₄, R₇, R₈, R₉, R₁₀, R₁₂, R₁₃, R₁₆, R₁₇and R₂₃ are, for example, acetylamino, propionylamino or butyrylamino,in particular acetylamino.

Halogen radicals R₄, R₇, R₈, R₉, R₁₀, R₁₂, R₁₃, R₁₆, R₁₇ and R₂₃ are,for example, fluorine or bromine, and in particular chlorine.

An N-mono- or N,N-di-C₁ -C₄ alkylamino radical R₂ is, for example, sucha group with methyl or ethyl radicals. N-Mono-C₁ -C₄ alkylamines arepreferred, for example --NHC₂ H₅ or, in particular, --NHCH₃.

Substituted or unsubstituted phenylamino R₁ is, in addition to theunsubstituted radicals, for example, the radicals substituted in thephenyl ring by C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino,ureido, halogen or sulfo. Phenylamino which is unsubstituted orsubstituted in the phenyl ring by C₁ -C₄ alkyl, C₁ -C₄ alkoxy orhalogen, in particular unsubstituted or substituted in the phenyl ringby C₁ -C₄ alkyl or C₁ -C₄ alkoxy, is preferred. The phenylamino radicalis particularly preferably unsubstituted.

R₁ is preferably hydrogen or phenylamino, in particular hydrogen.

R₂ is preferably hydrogen or amino.

Azo dyes of the formula (1) which are of particular interest are thosein which R₁, R₂ and R₃ are hydrogen.

Azo dyes of the formula (1) which are of special interest arefurthermore those in which

R₁ is hydrogen,

R₂ is amino and

R₃ is hydroxyl. R₄ is preferably hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy,C₂ -C₄ alkanoylamino or ureido, in particular hydrogen, C₁ -C₄ alkyl, C₁-C₄ alkoxy or ureido, preferably hydrogen.

Preferred radicals K of the formula (2) are those in which

R₅ and R₆ independently of one another are hydrogen or C₁ -C₄ alkylwhich is unsubstituted or substituted by hydroxyl or phenyl, in whichthe phenyl radical is unsubstituted or substituted by sulfo, and

R₇ and R₈ independently of one another are hydrogen, C₁ -C₄ alkyl or C₁-C₄ alkoxy.

Preferred radicals K of the formula (3) are those in which

Y is hydrogen or C₁ -C₄ alkyl, in particular hydrogen, and

R₉ and R₁₀ independently of one another are hydrogen, C₁ -C₄ alkyl or C₁-C₄ alkoxy.

Preferred radicals K of the formula (4) are those in which

R₁₁ is hydrogen, C₁ -C₄ alkyl or phenyl and

R₁₂ is hydrogen or hydroxyl.

Preferred radicals K of the formula (5) are those in which

R₁₃ is hydrogen.

Preferred radicals K of the formula (7) are those in which

R₁₄ is hydroxyl,

R₁₅ is methyl and

R₁₆ and R₁₇ independently of one another are hydrogen, C₁ -C₄ alkyl, C₁-C₄ alkoxy or sulfo.

Preferred radicals K of the formula (8) are those in which

R₁₈ is C₁ -C₄ alkyl,

R₁₉ is cyano or carbamoyl and

R₂₀ is C₁ -C₄ alkyl.

Preferred radicals K of the formula (9) are those in which

R₂₁ is C₁ -C₈ alkyl,

R₂₂ is hydrogen and

R₂₃ is hydrogen.

K is particularly preferably a radical of the formula (3), (4), (6),(7), (8) or (9), in particular a radical of the formula (3), (4) or (6),and preferably a radical of the formula (4) or (6). K is especiallypreferably a radical of the formula (4).

Preferred azo dyes are those of the formula ##STR11## in which R₄ and Kare as defined and preferred above.

Azo dyes which are furthermore preferred are those of the formula##STR12## in which R₄ and K are as defined and preferred above.

Preferably, in the azo dyes of the formulae (10) and (11),

R₄ is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino orureido and

K is a radical of the formula (3), (4) or (6), in particular a radicalof the formula (4) or (6).

Azo dyes of the formula (10) are of particular interest.

The present invention furthermore relates to a process for thepreparation of azo dyes of the formula (1), which comprises diazotizingan amine of the formula ##STR13## and coupling the diazotization productto a coupling component of the formula

    H--K                                                       (13)

or

diazotizing an amine of the formula ##STR14## and coupling thediazotization product to a coupling component of the formula ##STR15## aconversion reaction being carried out, if appropriate, after thereaction of the compounds of the formulae (12) and (13) or of thecompounds of the formulae (14) and (15), and R₁, R₂, R₃, R₄ and K beingas defined under formula (1).

The diazotization is in each case carried out in a manner known per se,for example with a nitrite, for example with an alkali metal nitrite,such as sodium nitrite, in a mineral acid medium, for example in ahydrochloric acid medium, at temperatures of, for example, -5° to 30°C., and preferably at 0° to 10° C.

The coupling is in each case carried out in a manner known per se atacid, neutral to weakly alkaline pH values and at temperatures of, forexample, -5° to 30° C., preferably 0° to 25° C.

If appropriate, an alkylation, for example, can also be carried out as aconversion reaction after the preparation of the azo dye. Thus, forexample, a hydroxyl group bonded to an aromatic radical can bealkylated, for example by alkylation with dialkyl sulfate, dialkylcarbonate, dialkyl methanephosphonate or methyl toluenesulfonatederivatives. The alkylation is carried out, for example, in aqueoussolution by a procedure known per se.

The compounds of the formulae (12), (13), (14) and (15) are known or canbe prepared analogously to known compounds.

The dyes of the formula (1) are present either in the form of their freeacid or, preferably, as salts thereof.

Suitable salts are, for example, the alkali metal or ammonium salts orthe salts of an organic amine.

Examples are the sodium, lithium, potassium or ammonium salts or thesalt of mono-, di- or triethanolamine.

The azo dyes of the formula (1) according to the invention are suitablefor dyeing and printing, in particular of fibre materials containingnitrogen or hydroxyl groups, paper or leather, for example textile fibrematerials of cellulose, silk and, in particular, wool and syntheticpolyamides, by methods known per se. The azo dyes of the formula (1)according to the invention can be used for dyeing or printing in thegenerally customary form, which has been worked up beforehand ifappropriate. Level dyeings with good all-round fastness properties, inparticular good fastness to rubbing, wet processing, wet rubbing andlight, are obtained. The dyes according to the invention furthermorehave a very good exhaustion capacity. The dyes according to theinvention moreover show a very good build-up capacity and can veryreadily be combined with other dyes. The abovementioned textile materialcan be in widely varying forms of processing, for example as fibre,yarn, woven fabric or knitted fabric.

In the following examples, parts are parts by weight. The temperaturesare degrees Celsius. Parts by weight bear the same relation to parts byvolume as the gram to the cubic centimeIre.

Preparation Example 1

34.5 parts of p-nitroaniline are diazotized with sodium nitrite underhydrochloric acid conditions in the customary manner.

The diazo solution thus prepared is added at room temperature to asuspension which comprises 59.8 parts of 2amino-8-naphthol-6-sulfonicacid and 250 parts of water. The coupling reaction is allowed to proceedto completion for 20 hours and the pH is then brought to a value of 9.5by means of aqueous sodium hydroxide solution (30%). A suspension whichcomprises the compound, shown in the form of the free acid, of theformula ##STR16## is obtained

1000 parts of the suspension thus obtainable are heated to a temperatureof 55° C. and 39 parts of sodium sulfide are added. The solution formedis subsequently stirred at a temperature of 72° to 75° C. for 15 minutesand then clarified by filtration. After addition of 90 parts of anaqueous sodium hydroxide solution (30%), the resulting precipitate isfiltered off after some time, washed with aqueous sodium chloridesolution (15%) and dried in vacuo at a temperature of 50° to 60° C. 83parts of a compound which, in the form of the free acid, has the formula##STR17## are obtained.

The compounds of the formulae ##STR18## can be obtained in an analogousmanner to Preparation Example 1.

Preparation Example 2

After stirring into 200 parts of water and 50 parts of hydrochloric acid(32%), 30 parts of 4-aminoacetanilide are diazotized with 50 parts of a4 normal sodium nitrite solution at a temperature of 5° to 10° C. Excessnitrite is destroyed with a little sulfamic acid.

The diazo solution thus prepared is allowed to run into a secondsolution which comprises 59.9 parts of phenyl-peri acid and 600 parts ofwater and is brought to a pH of 8 with aqueous sodium hydroxidesolution. While the diazo solution is running in, the pH is kept at avalue of 8 to 9 by addition of aqueous sodium hydroxide solution. Theresulting compound is then precipitated out by addition of sodiumchloride, washed with aqueous sodium chloride solution and dried invacuo at a temperature of 50° to 60° C. 102 parts of a compound which,in the form of the free acid, has the formula ##STR19## are obtained.

100 parts of the compound of the formula (109) obtainable as describedabove are hydrolyzed at the boil in 225 parts of water and 112 parts ofan aqueous sodium hydroxide solution (30%). The resulting mass isdiluted with water, filtered hot and washed with aqueous sodium chloridesolution (15%). After drying in vacuo at a temperature of 50° to 60° C.,75 parts of a compound which, in the form of the free acid, has theformula ##STR20## are obtained.

The compounds of the formulae ##STR21## can be obtained in an analogousmanner to Preparation Example 2.

Preparation Example 3

11.14 parts of 1-naphthylamine-5-sulfonic acid are dissolved in 100parts of water at room temperature and at a pH of 7 to 8. After additionof 12.5 parts of 4 normal sodium nitrite solution, the solution thusobtained is added dropwise to a mixture comprising 100 parts of ice and12.5 parts of hydrochloric acid (32%). After some time, excess nitriteis destroyed with sulfamic acid.

To prepare a second solution, 10.85 parts of2-methoxyanilinomethanesulfonic acid are dissolved in 100 parts of waterat a pH of 8. After admixing 6.3 parts of sodium bicarbonate, the diazocomponent solution obtainable as described above is added dropwise andthe pH is kept at a value of 6.5 to 7 by addition of a further 1.8 partsof sodium bicarbonate. The resulting compound is then precipitated outby addition of sodium chloride and filtered off. 72 parts of a compoundwhich, in the form of the free acid, has the formula ##STR22## areobtained.

72 parts of the compound of the formula (113) obtainable as describedabove are stirred in 200 parts of water, and 20 parts of sodiumhydroxide are added. After hydrolysis at the boiling point, a pH of 10is established with 45 parts of hydrochloric acid (32%), and theresulting compound is filtered off at room temperature, washed with anaqueous sodium chloride solution and dried in vacuo at a temperature of50° to 60° C. 16 parts of a compound which, in the form of the freeacid, has the formula ##STR23## are obtained.

The compounds of the formula ##STR24## can be obtained in an analogousmanner to Preparation Example 3.

EXAMPLE 1

3.58 parts of the compound of the formula ##STR25## are dissolved in 50parts of hot water under neutral conditions and 2.5 parts of a 4 normalsodium nitrite solution are added. The solution thus obtained is addedto a mixture of 50 parts of ice and 3 parts of hydrochloric acid (32%).After some time, the excess nitrite is destroyed with sulfamic acid.

The diazo component suspension thus obtained is added to a secondsolution which comprises 0.94 part of phenol and 50 parts of water. A pHof 9 is maintained during this procedure by addition of an aqueoussodium hydroxide solution. When the coupling has ended, the dye whichhas precipitated out is filtered off, washed with dilute sodium chloridesolution and dried in vacuo at a temperature of 50° to 60° C. 4.3 partsof a dye which, in the form of the free acid, is the compound of theformula ##STR26## are obtained. The dye of the formula (118) dyes wooland synthetic polyamide fibre material in claret-red colour shades.

EXAMPLES 2 to 139

The dyes shown in the form of the free acid in column 2 in the followingTable 1 can be obtained analogously to the instructions in Example 1.The dyes shown in column 2 in Table 1 dye wool and synthetic polyamidefibre material in the colour shades shown in column 3 in Table 1.

                                      TABLE 1                                     __________________________________________________________________________    Example                                                                            Dye                                        Color shade                   __________________________________________________________________________          ##STR27##                                 Claret                        3                                                                                   ##STR28##                                 Blue                          4                                                                                   ##STR29##                                 Blue                          5                                                                                   ##STR30##                                 Blue                          6                                                                                   ##STR31##                                 Blue                          7                                                                                   ##STR32##                                 Violet                        8                                                                                   ##STR33##                                 Violet                        9                                                                                   ##STR34##                                 Violet                        10                                                                                  ##STR35##                                 Blue                          11                                                                                  ##STR36##                                 Blue                          12                                                                                  ##STR37##                                 Blue                          13                                                                                  ##STR38##                                 Blue                          14                                                                                  ##STR39##                                 Claret                        15                                                                                  ##STR40##                                 Claret                        16                                                                                  ##STR41##                                 Claret                        17                                                                                  ##STR42##                                 Claret                        18                                                                                  ##STR43##                                 Blue                          19                                                                                  ##STR44##                                 Claret                        20                                                                                  ##STR45##                                 Violet                        21                                                                                  ##STR46##                                 Claret                        22                                                                                  ##STR47##                                 Blue                          23                                                                                  ##STR48##                                 Blue                          24                                                                                  ##STR49##                                 Blue                          25                                                                                  ##STR50##                                 Violet                        26                                                                                  ##STR51##                                 Violet                        27                                                                                  ##STR52##                                 Blue                          28                                                                                  ##STR53##                                 Blue                          29                                                                                  ##STR54##                                 Blue                          30                                                                                  ##STR55##                                 Blue                          31                                                                                  ##STR56##                                 Claret                        32                                                                                  ##STR57##                                 Claret                        33                                                                                  ##STR58##                                 Blue                          34                                                                                  ##STR59##                                 Blue                          35                                                                                  ##STR60##                                 Blue                          36                                                                                  ##STR61##                                 Blue                          37                                                                                  ##STR62##                                 Violet                        38                                                                                  ##STR63##                                 Violet                        39                                                                                  ##STR64##                                 Blue                          40                                                                                  ##STR65##                                 Blue                          41                                                                                  ##STR66##                                 Red                           42                                                                                  ##STR67##                                 Red                           43                                                                                  ##STR68##                                 Scarlet                       44                                                                                  ##STR69##                                 Scarlet                       45                                                                                  ##STR70##                                 Red                           46                                                                                  ##STR71##                                 Red                           47                                                                                  ##STR72##                                 Claret                        48                                                                                  ##STR73##                                 Claret                        49                                                                                  ##STR74##                                 Scarlet                       50                                                                                  ##STR75##                                 Scarlet                       51                                                                                  ##STR76##                                 Claret                        52                                                                                  ##STR77##                                 Red                           53                                                                                  ##STR78##                                 Claret                        54                                                                                  ##STR79##                                 Claret                        55                                                                                  ##STR80##                                 Scarlet                       56                                                                                  ##STR81##                                 Scarlet                       57                                                                                  ##STR82##                                 Claret                        58                                                                                  ##STR83##                                 Red                           59                                                                                  ##STR84##                                 Violet                        60                                                                                  ##STR85##                                 Claret                        61                                                                                  ##STR86##                                 Claret                        62                                                                                  ##STR87##                                 Blue                          63                                                                                  ##STR88##                                 Blue                          64                                                                                  ##STR89##                                 Blue                          65                                                                                  ##STR90##                                 Blue                          66                                                                                  ##STR91##                                 Claret                        67                                                                                  ##STR92##                                 Claret                        68                                                                                  ##STR93##                                 Blue                          69                                                                                  ##STR94##                                 Blue                          70                                                                                  ##STR95##                                 Red                           71                                                                                  ##STR96##                                 Red                           72                                                                                  ##STR97##                                 Scarlet                       73                                                                                  ##STR98##                                 Scarlet                       74                                                                                  ##STR99##                                 Red                           75                                                                                  ##STR100##                                Violet                        76                                                                                  ##STR101##                                Yellow                        77                                                                                  ##STR102##                                Yellow                        78                                                                                  ##STR103##                                Violet                        79                                                                                  ##STR104##                                Yellow                        80                                                                                  ##STR105##                                Yellow                        81                                                                                  ##STR106##                                Violet                        82                                                                                  ##STR107##                                Yellow                        83                                                                                  ##STR108##                                Yellow                        84                                                                                  ##STR109##                                Blue                          85                                                                                  ##STR110##                                Orange                        86                                                                                  ##STR111##                                Orange                        87                                                                                  ##STR112##                                Blue                          88                                                                                  ##STR113##                                Orange                        89                                                                                  ##STR114##                                Orange                        90                                                                                  ##STR115##                                Blue                          91                                                                                  ##STR116##                                Orange                        92                                                                                  ##STR117##                                Orange                        93                                                                                  ##STR118##                                Blue                          94                                                                                  ##STR119##                                Orange                        95                                                                                  ##STR120##                                Blue                          96                                                                                  ##STR121##                                Orange                        97                                                                                  ##STR122##                                Orange                        98                                                                                  ##STR123##                                Blue                          99                                                                                  ##STR124##                                Orange                        100                                                                                 ##STR125##                                Orange                        101                                                                                 ##STR126##                                Blue                          102                                                                                 ##STR127##                                Orange                        103                                                                                 ##STR128##                                Orange                        104                                                                                 ##STR129##                                Blue                          105                                                                                 ##STR130##                                Orange                        106                                                                                 ##STR131##                                Orange                        107                                                                                 ##STR132##                                Blue                          108                                                                                 ##STR133##                                Orange                        109                                                                                 ##STR134##                                Orange                        110                                                                                 ##STR135##                                Blue                          111                                                                                 ##STR136##                                Orange                        112                                                                                 ##STR137##                                Orange                        113                                                                                 ##STR138##                                Blue                          114                                                                                 ##STR139##                                Orange                        115                                                                                 ##STR140##                                Orange                        116                                                                                 ##STR141##                                Blue                          117                                                                                 ##STR142##                                Orange                        118                                                                                 ##STR143##                                Orange                        119                                                                                 ##STR144##                                Blue                          120                                                                                 ##STR145##                                Orange                        121                                                                                 ##STR146##                                Orange                        122                                                                                 ##STR147##                                Violet                        123                                                                                 ##STR148##                                Yellow                        124                                                                                 ##STR149##                                Orange                        125                                                                                 ##STR150##                                Violet                        126                                                                                 ##STR151##                                Yellow                        127                                                                                 ##STR152##                                Orange                        128                                                                                 ##STR153##                                Violet                        129                                                                                 ##STR154##                                Yellow                        130                                                                                 ##STR155##                                Orange                        131                                                                                 ##STR156##                                Violet                        132                                                                                 ##STR157##                                Yellow                        133                                                                                 ##STR158##                                Orange                        134                                                                                 ##STR159##                                Violet                        135                                                                                 ##STR160##                                Yellow                        136                                                                                 ##STR161##                                Orange                        137                                                                                 ##STR162##                                Violet                        138                                                                                 ##STR163##                                Yellow                        139                                                                                 ##STR164##                                Orange                        140                                                                                 ##STR165##                                Violet                        141                                                                                 ##STR166##                                Violet                        142                                                                                 ##STR167##                                Blue                          143                                                                                 ##STR168##                                Blue                          144                                                                                 ##STR169##                                Violet                        145                                                                                 ##STR170##                                Violet                        146                                                                                 ##STR171##                                Violet                        147                                                                                 ##STR172##                                Violet                        148                                                                                 ##STR173##                                Blue                          149                                                                                 ##STR174##                                Blue                          150                                                                                 ##STR175##                                Blue                          151                                                                                 ##STR176##                                Blue                          152                                                                                 ##STR177##                                Blue                          153                                                                                 ##STR178##                                Blue                          154                                                                                 ##STR179##                                Blue                          155                                                                                 ##STR180##                                Blue                          __________________________________________________________________________

EXAMPLE 156

5.37 parts of the compound of the formula ##STR181## are dissolved in 50parts of hot water under neutral conditions and 2.5 parts of a 4 normalsodium nitrite solution are added. The solution thus obtained is addedto a mixture of 50 parts of ice and 3 parts of hydrochloric acid (32%).After some time, the excess nitrite is destroyed with sulfamic acid.

The diazo component suspension thus obtained is added to a secondsolution which comprises 4.49 parts of phenyl-peri acid and 60 parts ofwater, the pH of which is adjusted to neutral. A pH of 7 is maintainedduring this procedure by addition of an aqueous sodium hydroxidesolution. When the coupling has ended, the dye is precipitated out byaddition of methanol. The pH is then brought to a value of 11 and thedye is filtered off, washed with dilute sodium chloride solution anddried in vacuo at a temperature of 50° to 60° C. 7.5 parts of a dyewhich, in the form of the free acid, is the compound of the formula##STR182## are obtained. The dye of the formula (119) dyes wool andsynthetic polyamide fibre material in blue colour shades.

EXAMPLES 157 to 159

The procedure described in Example 156 is repeated, but using a compoundof the formula ##STR183## instead of a compound of the formula (102).Analogous dyestuffs which dye wool and synthetic polyamide fibrematerial in violet-blue colour shades are obtained.

EXAMPLE 160

2.13 parts of the compound of the formula ##STR184## are dissolved in 25parts of water at room temperature with the addition of 5.5 parts of 2normal aqueous sodium hydroxide solution, and 2.5 parts of a 4 normalsodium nitrite solution are added. The solution is added dropwise to amixture of 25 parts of ice and 3.5 parts of hydrochloric acid (32 %).After some time, the excess nitrite is destroyed with sulfamic acid.

The diazo component suspension thus obtained is allowed to run at roomtemperature into a second solution which comprises 3 parts ofphenyl-peri acid and 50 parts of water, the pH of which is brought toneutral While the suspension of the diazo component is running in, thepH is kept at a value of 7 to 8 by addition of 2 normal aqueous sodiumhydroxide solution. The resulting dye is precipitated out by addition ofsodium chloride, filtered off, washed with dilute sodium chloridesolution and dried in vacuo at a temperature of 50° to 60° C. 3.8 partsof a dye which, in the form of the free acid, is the compound of theformula ##STR185## are obtained. The dye of the formula (124) dyes wooland synthetic polyamide fibre material in claret-red colour shades.

5 parts of the dye of the formula (124) are dissolved in 100 parts ofwater at a temperature of 70° to 75° C and a pH of 9. Diethyl sulfate isthen added dropwise, the pH being kept at a value of 9 by addition of 2normal sodium hydroxide solution. When the end of the alkylation isdetected by thin layer chromatography, the dye which has precipitatedout is filtered off, washed with dilute sodium chloride solution anddried in vacuo at a temperature of 50° to 60° C. 2.6 parts of a dyewhich, in the form of the free acid, is the compound of the formula##STR186## are obtained. The dye of the formula (125) dyes wool andsynthetic polyamide fibre material in violet colour shades.

EXAMPLE 161

The dye of the formula ##STR187## can be obtained analogously to theinstructions in Example 160. The dye of the formula (126) dyes wool andsynthetic polyamide fibre material in violet colour shades.

Dyeing instructions I:

10 parts of Helanca tricot are dyed in 500 parts of an aqueous liquorwhich comprises 1 g/l of monosodium phosphate and is brought to pH 6with disodium phosphate. The content of the dye according to Example 1is 0.8%, based on the fibre weight. The dyeing time at a temperature of98° C. is 30 to 90 minutes. The dyed piece of Helanca is then removedfrom the liquor and washed and dried in the customary manner. A piece ofHelanca which has been dyed claret-red and has good overall fastnessesis obtained.

Dyeing instructions II:

10 parts of wool knitting yam are stirred at 50° C. into a dyebath whichcomprises 400 parts of water, 0.4 part of the dye according to Example 1and 5 parts of sodium sulfate and is brought to a pH of 5 with aceticacid. The liquor is brought to the boiling point in the course of 45minutes and kept at the boiling point for a further 45 minutes. The dyedgoods are then removed, rinsed thoroughly with cold water and dried. Aclaret-red dyeing on wool with good fastness properties is obtained.

What is claimed is:
 1. An azo dye of the formula ##STR188## in which R₁is hydrogen or substituted or unsubstituted phenylamino,R₂ is hydrogen,amino or N-mono- or N,N-di-C₁ -C₄ alkylamino, R₃ is hydrogen orhydroxyl, R₄ is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄alkanoylamino, ureido or halogen an K is a radical of the formula##STR189## in which Y is hydrogen or C₁ -C₄ alkyl which is unsubstitutedor substituted by hydroxyl and R₉ and R₁₀ independently of one anotherare hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino, ureido,halogen or sulfo;or a radical of the formula ##STR190## in which R_(H)is hydrogen, C₁ -C₄ alkyl or phenyl which is unsubstituted orsubstituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino,ureido, halogen or sulfo and R₁₂ is hydrogen, C₁ -C₄ alkyl, C₁ -C₄alkoxy, C₂ -C₄ alkanoylamino, ureido, halogen or hydroxyl;or a radicalof the formula ##STR191## in which R₁₃ is hydrogen, C₁ -C₄ alkyl, C₁ -C₄alkoxy, C₂ -C₄ alkanoylamino, ureido or halogen; or a radical of theformula ##STR192## or a radical of the formula ##STR193## in which R₁₄is amino or hydroxyl, R₁₅ is methyl or carboxyl and R₁₆ and R₁₇independently of one another are hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy,C₂ -C₄ alkanoylamino, ureido, halogen or sulfo;or a radical of theformula ##STR194## in which R₁₈ is hydrogen or C₁ -C₄ alkyl, R₁₉ iscyano, carbamoyl or sulfomethyl and R₂₀ is hydrogen, C₁ -C₄ alkyl orphenyl which is unsubstituted or substituted by C₁ -C₄ alkyl, C₁ -C₄alkoxy, C₂ -C₄ alkanoylamino, ureido, halogen or sulfo;or a radical ofthe formula ##STR195## in which R₂₁ is hydrogen, C₁ -C₈ alkyl or phenylwhich is unsubstituted or substituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂-C₄ alkanoylamino, ureido, halogen or sulfo, R₂₂ is hydrogen or C₁ -C₈alkyl and R₂₃ is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄alkanoylamino, ureido, halogen or sulfo;and the azo dye of the formula(1) comprises at least one and not more than two sulfo groups, with theproviso that if K is a radical of the formula (3), the radical R₄ ishydrogen.
 2. An azo dye according to claim 1, in whichR₁ is hydrogen. 3.An azo dye according to claim 1, in whichR₂ is hydrogen or amino.
 4. Anazo dye according to claim 1, in whichR₄ is hydrogen, C₁ -C₄ alkyl, C₁-C₄ alkoxy, C₂ -C₄ alkanoylamino or ureido.
 5. An azo according to claim1, in whichK is a radical of the formula (3), (4) or (6).
 6. An azo dyeaccording to claim 1, in whichK is a radical of the formula (4) or (6).7. An azo dye according to claim 1, of the formula ##STR196## in whichR₄ and K are as defined in claim
 1. 8. An azo dye according to claim 7,in whichR₄ is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄alkanoylamino or ureido and K is a radical of the formula (3), (4) or(6).
 9. An azo dye according to claim 1, of the formula ##STR197## inwhich R₄ and K are as defined in claim
 1. 10. An azo dye according toclaim 9, in whichR₄ is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄alkanoylamino or ureido and K is a radical of the formula (3), (4) or(6).
 11. A process for the preparation of an azo dye according to claim1, which comprises diazotizing an amine of the formula ##STR198## andcoupling the diazotization product to a coupling component of theformula

    H--K                                                       (13)

or diazotizing an amine of the formula ##STR199## and coupling thediazotization product to a coupling component of the formula ##STR200##a conversion reaction being carried out, if appropriate, after thereaction of the compounds of the formulae (12) and (13) or of thecompounds of the formulae (14) and (15), and R₁, R₂, R₃, R₄ and K beingas defined in claim
 1. 12. A process for dyeing or printing fibrematerial containing hydroxyl groups or nitrogen, which process comprisesthe step of applying to said fibre material a tinctorial amount of anazo dye according to claim
 1. 13. A process according to claim 12wherein said fibre material is naturally occurring or syntheticpolyamide fibre material.